Sunscreen compositions

ABSTRACT

Sunscreen compositions comprising one or more sunscreen agents (inorganic and combinations of inorganic and organic), one or more film forming polymers (synthetic or naturally derived), and heat treated xanthan gum. The sunscreen composition provides higher pre- and post-immersion SPF values, as well as a means for reducing the amount of sunscreen agents in a formulation without forfeiting efficacy.

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention is directed towards skincare compositions. Moreparticularly, the present invention is directed towards sunscreencompositions having improved efficacy in protection from ultravioletradiation.

2. Background Information

Consumers are increasingly concerned about the effects of ultraviolet(‘UV’) radiation on the skin, and with good reason. Skin cancer hasbecome one of the leading forms of cancer, annually affecting millionsglobally. Demand for UV protection has made the sun care market one ofthe fastest growing personal care sectors.

Commercially viable sun care products should provide a variety ofbenefits, such as high Sun Protection Factor (SPF) values, protectionfrom UV-A and UV-B radiation (also known as broad-spectrum protection),water resistance and rub-off resistance, aesthetically pleasingproducts, and convenient application.

When formulating these products, consumer use should be considered. Forexample, swimming or mild perspiration is often sufficient to removemost commercially available sunscreen formulations from a person's skin,necessitating multiple applications. Such repeated applications areinconvenient, costly and typically results in the consumer delayingreapplication of the sunscreen, which may lead to sunburn.

Accordingly, higher SPF values, broad spectrum protection, enhancedwater and rub-off resistance, the need for aesthetically pleasingproducts, and convenience have become increasingly important in sunprotection formulations. Further, formulators continue to search forways to not only increase the SPF value of formulations, but also toincrease the efficacy of a sunscreen without increasing the actual levelof the sunscreen actives within the formulation.

Additionally, formulators are left with little choice in the type ofrheology modifiers used in formulations, particularly those containingactives (or agents) such as inorganic particulate sunscreen agents.Historically, xanthan gum has been the thickener of choice; however,this thickener contributes no benefit with respect to SPF enhancement.

Film forming polymers are used widely in personal care products forfunctions such as hair fixatives, SPF retention, water resistance,rub-off resistance, fragrance retention, and so forth and are well knownin the art. These polymers can be both synthetic and naturally derived.The polymers are typically used in a variety of applications, includingsun protection, to enhance the water and rub-off resistance of the UVfilters. With the advent of higher SPF products, the challenge has beento create these sun protection formulations without increasing eitherthe use level of the polymer or UV filters or both. Doing so causesunpleasant aesthetics and increased cost.

Therefore, there is a need for a sunscreen formulation that providesboth water resistance and higher SPE values when applied to a person,both before and after immersion in water, in particular, one thatprovides these benefits without the need to increase the amount ofsunscreen active or agent.

SUMMARY OF THE INVENTION

According to the present invention, a synergy has been discoveredbetween heat-treated xanthan gum (e.g., xanthan gum having an INCIdesignation ‘dehydroxanthan gum’) and film forming polymers that resultsin SPF enhancement. This enhancement allows for higher SPF values bothbefore and after water immersion. This synergy also allows for thereduction of amount of sunscreen agents used in a formulation withoutsacrificing SPF efficacy. Thus, this synergistic combination of UVfilter, polymer, and heat treated xanthan gum results in a very usefultool to create higher SPF sun protection and cosmetic formulations.

“Synergistic” for the purpose of the present invention refers to theaction of two or more substances achieving an effect greater than thatpossible with any of the individual components (i.e., the sum beinggreater than the parts).

“Heat treated” for the purpose of the present invention refers toxanthan gum that is heated for a given temperature and time. An examplewould be xanthan gum that is heated at 60° C. for at least 30 minutes tomoisture content of less than about 8%.

Accordingly, the present invention provides in one aspect a sunscreencomposition that is formulated with at least one or more sunscreenactives, with one or more of sunscreen actives being at least oneinorganic sunscreen active. The composition further includes one or morefilm forming polymers and heat treated xanthan gum. With the one or morefilm forming polymers and heat treated xanthan gum, sunscreencompositions in one aspect provide a higher SPF value in suchcompositions than sunscreen compositions wherein the heat treatedxanthan gum is replaced with non-heat treated xanthan gum.

In one aspect, sunscreen compositions according to the present inventioninclude one or more sunscreen actives present in an amount of about 0.25to about 30% by weight, based on total weight of the composition. In afurther aspect, the one or more sunscreen actives include one or moreparticulate sunscreen actives. In even another aspect, the one or moreparticulate sunscreen actives is at least an inorganic sunscreen activesuch as zinc oxide and/or titanium dioxide. In one aspect, sunscreencompositions according to the present invention include at least one ormore inorganic sunscreen actives in a water phase of the composition.

In one embodiment, sunscreen composition according to the presentinvention include one or more sunscreen actives wherein at least one ofthe actives is at least one or more particulates chosen from, forexample, clays, agars, guars, nanoparticles, native and modifiedstarches, modified cellulosics, zinc oxide, titanium dioxide andcombinations thereof. In another embodiment, sunscreen compositionsaccording to the present invention include one or more modified starchessuch as octenyl succinate (OSA) modified starch, modified corn starchand combinations thereof. In even another embodiment, sunscreencompositions according to the present invention include one or moresunscreen actives wherein at least one of the actives is an organicsunscreen active. In another aspect, sunscreen composition according tothe present invention include one or more organic sunscreen activeschosen from, for example, ethylhexyl methoxycinnamate (octinoxate),ethylhexyl salicylate (octisalate), butylmethoxydibenzoylmethane,methoxydibenzoylmethane, avobenzone, benzophenone-3 (oxybenzone),octocrylene, aminobenzoic acid, cinoxate, dioxybenzone, homosalate,menthyl anthranilate, octocrylene, octisalate, oxybenzone, padimate O,phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylateand combinations thereof.

In one aspect, sunscreen compositions according to the present inventioninclude one or more film forming polymers present in an amount of about0.05 to about 10% by weight, based on total weight of the composition.In another aspect, sunscreen compositions according to the presentinvention include one or more film forming polymers wherein at least oneof the polymers is an acrylates copolymer. In even another aspect,sunscreen compositions according to the present invention include one ormore film forming polymers wherein at least one of the polymers is apolyurethane copolymer.

In one aspect, sunscreen compositions according to the present inventioninclude heat treated xanthan gum present in an amount of about 0.05 toabout 20% by weight, based on total weight of the composition.

In one embodiment, sunscreen compositions according to the presentinvention are in the form of an oil-in-water emulsion.

Sunscreen compositions according to the present invention can furtheroptionally include one or more active agents. Non-limiting examples ofsuch actives include anti-acne agents, antimicrobial agents,anti-inflammatory agents, analgesics, anti-erythemal agents, antiruriticagents, antiedermal agents, antipsoriatic agents, antifungal agents,skin protectants, vitamins, antioxidants, scavengers, antiirritants,antibacterial agents, antiviral agents, antiaging agents,protoprotection agents, hair growth enhancers, hair growth inhibitors,hair removal agents, antidandruff agents, anti-seborrheic agents,exfoliating agents, wound healing agents, anti-ectoparacitic agents,sebum modulators, immunomodulators, hormones, botanicals, moisturizers,astringents, cleansers, sensates, antibiotics, anesthetics, steroids,tissue healing substances, tissue regenerating substances, amino acids,peptides, minerals, ceramides, hydroxyalkyl urea, biohyaluronic acids,vitamins, skin lightening agents, self tanning agents, coenzyme Q10,niacinimide, capcasin, caffeine, and combinations thereof.

In addition to the active agents, sunscreen compositions according tothe present invention can optionally include one or more adjuvants.Sunscreen compositions according to the present invention can alsooptionally include one or more conditioning agents. Likewise, sunscreencompositions according to the present invention can optionally includeone or more preservatives. Sunscreen compositions according to thepresent invention can further optionally include one or more aestheticenhancers. Non-limiting examples of such aesthetic enhancers includecorn starch, tapioca starch and combinations thereof. It will berecognized by one skilled in the art that any combination of theseoptional ingredients may be utilized in the present sunscreencompositions.

In even a further embodiment, the present invention includes a method ofreducing UV radiation on a substrate by applying to the substrate aneffective amount of a sunscreen composition formulated with at least oneor more sunscreen actives, with one or more of sunscreen actives beingat least one inorganic sunscreen active. The composition furtherincludes one or more film forming polymers and heat treated xanthan gum.

DETAILED DESCRIPTION

The present invention is directed to a composition comprising one ormore sunscreen actives or agents (including particulate and combinationsof particulate and organic), one or more water dispersible film formingpolymers (synthetic or naturally derived), and heat treated xanthan gum.These compositions are suitable in a variety of applications, includingthose found in cosmetic and personal care.

The hydrocolloid xanthan gum is a polysaccharide gum derived from thebacterium Xanthomonas and is well known in the art. It haspseudo-plastic or shear-thinning behavior characterized by a decrease inapparent viscosity in response to an increase in shear rate.

Xanthan gum is typically used as a rheology modifier in a variety ofindustrial applications, functioning in thickening, viscosifying andgelling. It has also been used to impart stability to emulsions and forits suspending properties to prevent the settling out of solids. Xanthangum's limited ability to be dispersed in either hot or cold waterrestricts its use in a broad variety of applications, includingpharmaceuticals, household products, foods, and personal care products.

Heat treated xanthan gums according to the present invention differ fromother xanthan gum in that they increase solution viscosity (at 1% solidsin an aqueous solution) at least about 10,000 cps compared to thesolution viscosity (at 1% solids in an aqueous solution) of xanthan gumprior to heat treatment. In another aspect, xanthan gums according tothe present invention provide an increase in solution viscosity of up toat least about 12,500 cps over the viscosity of xanthan gum prior totreatment. In even another aspect, xanthan gums according to the presentinvention increase solution viscosity up to at least about 15,000 cpsover the viscosity of xanthan gum prior to treatment, depending upon theheat treatment conditions used.

Heat treated xanthan gum typically has improved dispersibility overnon-heat treated gum, such that under given conditions of temperatureand agitation, the time to fully disperse the heat treated gum istypically reduced by 25% versus gums that are not heat treated. Inanother aspect, the time to fully disperse is reduced by 50%. In evenanother aspect, the time for the gum to disperse is reduced by 70%compared to non-heat treated xanthan. The heat treated gum alsogenerally provides improved thickening ability, rheology modification,emulsion stabilization, suspending ability, texture enhancement, filmforming and foam stabilization.

Heat treated xanthan gum provides clear to translucent clarity and iseasy to use as it is dispersible in either hot or cold water and needsno neutralization. It exhibits tolerance to salt and extreme pH,particularly in the range of about 2 to about 12, is biodegradable, andmay be labeled as natural.

Heat modification of xanthan gum improves the ease of use, includingease of dispersing in solution with fewer tendencies to form fish eyes.Heat modification also not only improves thickening efficiency, but alsoaesthetics such as gel texture, (e.g., reducing the stringiness orpituitousness of the long texture). In addition, the viscosity enhancingeffect of heat treated xanthan can occur in a variety of pH and saltranges. Heat treated xanthan gum is compatible with anionic, cationic ornonionic polymers, allowing it to be formulated with a variety ofcommonly used additives.

Xanthan gum that has been further processed by heat treatment is knownin the art. For example, European Publication No. 0 321 216 A describesenhancing the viscosity profile of xanthan gum by thermally treating it.Heat treatment of xanthan gum is also described in Japanese ApplicationNo. 8-193055, which heat treats xanthan gum in its powdered form. U.S.Publication No. 2003-0108505 A1 describes the use of heat treatedxanthan gum in hair cosmetics.

Any xanthan gum may be used as a starting material for heat treatment.Such xanthan gums are commercially available, for example, from ArcherDaniels Midland and CP Kelco. These gums typically have a moisturecontent of from 8 to about 14 weight %, based on total weight of thegum, with about 10-11 weight % being the average amount of moisture.

Heat treatment can be performed on xanthan gum to reduce its moisturecontent to less than about 8%. In another aspect, the gum can be heattreated so as to reduce its moisture content to less than about 5%. Ineven another aspect, xanthan gum can be heat treated so as to reduce itsmoisture content to less than about 1%, or substantially anhydrous. Heattreatment can occur at a temperature of at least about 60° C. The gumcan be heat treated, for example, for a period of time of about 30minutes to at least 2 hours, depending upon the level of moisture in thegum that is sought and the temperature at which the gum is heat treated.

Temperature and time of heat treatment can be adjusted by one skilled inthe art in order to achieve the desired viscosity, dispersibility, geltexture, solution clarity, and any other properties desired. Theseproperties are also dependent upon the xanthan gum starting materialused (e.g., its grade, viscosity, molecular weight, and particle size).

Heat treatment of xanthan gum can be accomplished by any of a variety ofmethods known in the art, including, without limitation, the use ofovens, fluidized beds, infrared and microwave heat treatments. Theparticle size of the resultant heat-treated xanthan gum can be adjustedusing methods known in the art such as milling, or the particle size canbe adjusted prior to heat treatment.

Heat treated xanthan gum according to the present invention canoptionally be further modified either before or after heat treatment.For example, the gum can be chemically, enzymatically or physicallymodified. Such processes are known in the art. Suitable chemicalmodifications include, for example, gum conversion by oxidation, enzymeconversion, acid hydrolysis, heat and/or acid dextrinization, or shear.Suitable chemical derivatives include esters, such as acetate, and halfesters, such as succinate, octenyl succinate and tetradecenyl succinate;phosphate derivatives; ethers such as hydroxyalkyl ethers and cationicethers; or any other derivatives or combinations thereof. Modificationcan also be by chemical crosslinking. Crosslinking agents suitable foruse herein include phosphorus oxychloride, epichlorohydrin, sodiumtrimetaphosphate and adipic-acetic mixed acid anhydrides. Suitableenzymatic treatments that produce additional derivatives are alsoincluded. Suitable processes for physical modification include, forexample, agglomeration, spray drying, drum drying, chilsonation, jetcooking and extrusion.

Heat treated xanthan gum according to the present invention can bepurified by any method known in the art to remove off flavors, colors,and contaminants that are native to the gum or are created during themodifications and/or heat treatment processes as long as the heattreatment is not substantially impacted.

Heat treated xanthan gum may be used in a variety of compositions,including without limitation, cosmetic and personal care compositions,detergents and household cleaning compositions, paper products, oilfield chemicals, and food and beverage compositions. Cosmetic andpersonal care compositions include skin lotions and creams, skin gels,serums and liquids, facial and body cleansing products, wipes, liquidand bar soap, color cosmetic formulations, make-ups, foundations, suncare products, sunscreens, sunless tanning formulations, shampoos,conditioners, hair color formulations, hair relaxers, products with AHAand BHA and hair fixatives such as sprays, gels, mousses, pomades, andwaxes, including low VOC hair fixatives and sunscreens. The compositionsmay be in any form, including without limitation, emulsions, gels,liquids, sprays, solids, mousses, powders, wipes, or sticks.

Heat treated xanthan gum may be formulated into compositions at anylevel which provides the desired properties. Typically, a lesser amountof heat-treated xanthan gum will be required to achieve the sameproperties and functionality as native or non-heat treated xanthan gum.Heat treated xanthan gums can be used in compositions in an amount of atleast about 0.05 to about 20% by weight, based on total weight of thecomposition. In another aspect, the heat treated gum is present in thecomposition in an amount of about 0.05% to about 5% by weight, based ontotal weight of the composition. The amount used will depend not onlyupon the properties desired, but also upon the degree of heat treatmentof the gum, as well as other ingredients in the composition.

Heat treated xanthan gum can be incorporated into the composition in thesame manner as native xanthan gum. For example, heat-treated xanthan gumcan be dispersed in water and then the remaining components added.

In addition to the heat treated xanthan gum, compositions according tothe present invention further include polymers and copolymers capable offorming a film. Useful film forming polymers can either be synthetic ornaturally derived. For example, film forming polymers according to thepresent invention include water dispersible polymers, either naturallyor synthetically derived, that, when added to water at about 5% solidsat about 22° C. and at a pH of about 5.5, do not give a clear solution.Like xanthan gums, film forming polymers can be used in a variety ofcompositions, for example, cosmetic and personal care compositions,detergents and household cleaning compositions, paper products, oilfield chemicals, and food and beverage compositions. Cosmetic andpersonal care compositions include, for example, skin lotions andcreams, skin gels, serums and liquids, facial and body cleansingproducts, wipes, liquid and bar soap, color cosmetic formulations,make-ups, foundations, sun care products, sunscreens, sunless tanningformulations, shampoos, conditioners, hair color formulations, hairrelaxers, products with AHA and BHA and hair fixatives such as sprays,gels, mousses, pomades, and waxes, including low VOC hair fixatives andsunscreens. These cosmetic and personal care compositions may be in anyform, including with out limitation, emulsions, gels, liquids, sprays,solids, mousses, powders, wipes, or sticks.

Non-limiting examples of synthetic, water dispersible film formingpolymers suitable for use in the present invention include: fromNational Starch and Chemical Company, AMPHOMER and AMPHOMER LV-71polymers (octylacrylamide/acrylates/butylaminoethyl methacrylatecopolymer), AMPHOMER HC polymer (acrylates/octylacrylamide copolymer)BALANCE 0/55 and BALANCE CR polymers (acrylates copolymer), BALANCE 47polymer (octylacrylamide/acrylates/butylaminoethyl methacrylatecopolymer), RESYN 28-2930 polymer (VA/crotonate/vinyl neodecanoatecopolymer), RESYN 28-1310 polymer (VA/Crotonate copolymer), DynamXpolymer (polyurethane-14 (and) AMP-Acrylates copolymer), RESYN XPpolymer (acrylates/octylacrylamide copolymer), STRUCTURE 2001(acrylates/steareth-20 itaconate copolymer) STRUCTURE 3001(acrylates/ceteth-20 itaconate copolymer), YODOSOL 32A707, YODOSOL GH15,YODOSOL GH32, YODOSOL GH33, YODOSOL GH34, YODOSOL GH35, YODOSOL GH256,YODOSOL GH800, YODOSOL GH810, YODOSOLGH32A707F, YODOSOL GH15F, YODOSOLGH34F, YODOSOL GH800F, YODOSOL GH810F, YODOSOL GH800PF (acrylatescopolymer), YODOSOL GH52, YODOSOL GH52-OP(styrene/methacrylamide/acrylates copolymer), YODOSOL GH265(polyacrylate-2), YODOSOL GH840, YODOSOL GH41F, YODOSOL GH4I(styrene/acrylates copolymer), YODOSOL PUD (polyurethane-10 (and) PEG-12dimethicone (and) alcohol), DERMACYL AQF (acrylates copolymer),DERMACRYL C (proposed: acrylates copolymer) and DERMACRYL 79 and LTpolymers (acylates/octyacrylamide copolymer); from ISP, OMNIREZ-2000(PVM/MA half ethyl ester copolymer), GANTREZ A-425 (butyl ester ofPVM/MA copolymer), GANTREZ AN-119 PVM/MA copolymer, GANTREZ ES 225(ethyl ester of PVM/MA copolymer), GANTREZ ES-425 (butyl ester of PVM/MAcopolymer), AQUAFLEX XL-30 (Polyimide-1), ALLIANZ LT-120 (Acrylates/C1-2Succinates/Hydroxyacrylates Copolymer), ALLIANZ OPT (Acrylates/C₁₂₋₂₂Alkyl Methacrylate Copolymer), STYLEZE CC-10 (PVP/DMAPA AcrylatesCopolymer), STYLEZE 2000 (VP/Acrylates/Lauryl Methacrylate Copolymer),STYLEZE W-20 (Polyquaternium-55), ADVANTAGE PLUS (VA/ButylMaleate/Isobornyl Acrylate Copolymer); from BASF, ULTRAHOLD STRONG(acrylic acid/ethyl acrylate/t-butyl acrylamide), LUVIMER 100 P (t-butylacrylate/ethyl acrylate/methacrylic acid), LUVIMER 36D (ethylacrylate/t-butyl acrylate/methacrylic acid), LUVISET PUR(Polyurethane-1), LUVISET Clear (VP/Methacrylamide/Vinyl ImidazoleCopolymer), LUVIFLEX SOFT (Acrylates Copolymer), ULTRAHOLD 8(Acrylates/Acrylamide Copolymer), LUVIFLEX Silk (PEG/PPG-25/25Dimethicone/Acrylates Copolymer), LUVISET CAN (VA/crotonate/vinylneodecanoate copolymer), LUVIMER PRO55 (acrylates copolymer); fromAmerchol, AMERHOLD DR-25 (acrylic acid/methacrylicacid/acrylates/methacrylates); from Rohm and Haas, ACUDYNE 258 (acrylicacid/methacrylic acid/acrylates/methacrylates/hydroxy ester acrylates),ACUDYNE DHR (acrylates/hydroxyesters acrylates copolymer) ALLIANZ OPT(Acrylates/C12-22 Alkyl Methacrylate Copolymer); from Mitsubishi anddistributed by Clariant, DIAFORMER Z-301, DIAFORMER Z-SM, and DIAFORMERZ-400 (methacryloyl ethyl betaine/acrylates copolymer), ACUDYNE 180(Acrylates/Hydroxyesters Acrylates Copolymer), ACUDYNE SCP(Ethylenecarboxyamide/AMPSA/Methacrylates Copolymer), and the ACCULYNrheological modifiers; from ONDEO Nalco, FIXOMER 40 (acrylatescopolymer), FIXOMER A-30 and FIXOMER N-28 (INCI names: methacrylicacid/sodium acrylamidomethyl propane sulfonate copolymer); from EastmanChemical, Eastman polymer AQ38S and AQ55S(diglycol/CHEM/isophthalates/SIP copolymer); from Interpolymer, SYNTRAN5009 AND SYNTRAN 5760 (Styrene/Acrylates/Ammonium MethacrylateCopolymer), SYNTRAN 5190 (acrylates copolymer), SYNTRAN 5900 and 5902(polystyrene), SYNTRAN 5903, 5904, 5905 (styrene/acrylates copolymer),SYNTRAN KL-219C (ammonium acrylates copolymer), SYNTRAN PC 5112(polyacrylate-16), SYNTRAN PC5208 (polyacrylate-15), SYNTRAN PC5100(Polyacrylate-21 and Acrylates/Dimethylaminoethyl MethacrylateCopolymer) SYNTRAN PC5107 and PC5117 (Polyacrylate-18 andPolyacrylate-19), SYNTRAN PC5205 and PC5227 (Polyacrylate-15 andPolyacrylate-17); from Noveon, FIXATE G-100 (AMP-Acrylates/AllylMethacrylate Copolymer), FIXATE PLUS (Polyacrylates-X), CARBOPOL Ultrez10 (Carbomer), CARBOPOL Ultrez 20 (Acrylates/C10-30 Alkyl AcrylatesCopolymer), AVALURE AC series (Acrylates Copolymer), AVALURE UR series(Polyurethane-2, Polyurethane-4, PPG-17/IPDI/DMPA Copolymer); fromInolex Chemical Company, LEXOREZ TL8 (Trimethylpentanediol/Adipic AcidCopolymer, LEXOREZ TC8 and LEXOREZ TC-1 (INCI names:Trimethylpentanediol/Adipic Acid/Isononanoic Acid Copolymer), LEXOREZ200 (Trimethylpentanediol/Adipic Acid/Glycerin Crosspolymer), LEXOREZ100 (Adipic Acid/Diethylene Glycol/Glycerin Crosspolymer), LEXFILM SUN(polyester-7 (and) neopentyl glycol diheptanoate), LEXFILM SPRAY(polyester-10 (and) propylene glycol dibenzoate); from Dow Corning: DOWCORNING FA 4002 ID SILICONE ACRYLATE (Isododecane (and)Acrylates/Polytrimethylsiloxymethacrylate Crosspolymer), DOW CORNINGFA4001 ID SILICONE ACRYLATE (Cyclopentasiloxane (and)Acrylates/Polytrimethylsiloxymethacrylate Copolymer); and anycombination of the foregoing. (For the purpose of the present invention,it is understood that the film forming polymers may be used in theirwater dispersible or water soluble state. For example, at least some ofthe above mentioned commercial film formers are not render water solublewith some degree of neutralization; otherwise they may be soluble onlyin organic solvent.)

Useful film forming polymers can further optionally include combinationsof other water dispersible synthetic polymers as well as ones naturallyderived, either alone or in combination. Natural film forming waterdispersible polymers suitable for use in the present invention includeany polysaccharide derivative (both native and modified). For example,native starch as used herein refers to starch as it is found in nature.Also suitable are starches derived from a plant obtained by standardbreeding techniques, including crossbreeding, translocation, inversion,transformation or any other method of gene or chromosome engineering toinclude variations thereof. In addition, starch derived from a plantgrown from artificial mutations and variations of the above genericcomposition that may be produced by known standard methods of mutationbreeding are also suitable herein.

Typical sources for the starches are cereals, tubers, roots, legumes andfruits. The native source can be corn, pea, potato, sweet potato,banana, barley, wheat, rice, sago, amaranth, tapioca, arrowroot, canna,sorghum, and waxy or high amylose varieties thereof. The term “waxy” isintended to refer to those starches containing at least about 95 percentby weight amylopectin (the remainder being amylose), and the term “highamylose” is intended to refer to those starches containing at leastabout 40 percent by weight amylose (the remainder being amylopectin). Inanother aspect, high amylose starch refers to those starches containingat least about 70 percent by weight amylose.

Modifications to native starches suitable for the present invention canbe performed using any modification known in the art, includingphysical, chemical and/or enzymatic modifications, to obtain the desiredfilm forming attributes.

Physically modified starches suitable for use herein include shearedstarches, thermally-inhibited starches described in the family ofpatents represented by International Publication No. WO 95/04082, andresistant starches described in the family of patents represented byU.S. Pat. No. 5,593,503.

Chemically modified starches include, without limitation, those whichhave been crosslinked, acetylated and organically esterified,hydroxyethylated and hydroxypropylated, phosphorylated and inorganicallyesterified, cationic, anionic, nonionic, amphoteric and zwitterionic,and succinate and substituted succinate derivatives thereof. Suchmodifications are known in the art, for example, in the text MODIFIEDSTARCHES: PROPERTIES AND USES, Würzburg, Ed., CRC Press, Inc., Florida(1986).

Conversion products derived from any of the starches, including fluidityor thin-boiling starches prepared by oxidation, enzyme conversion, acidhydrolysis, heat and or acid dextrinization, thermal and or shearedproducts may also be useful herein.

Further suitable are pregelatinized starches known in the art anddisclosed, for example, in U.S. Pat. Nos. 4,465,702, 5,037,929,5,131,953 and 5,149,799. Conventional procedures for pregelatinizingstarch are also known to those skilled in the art and described, forexample, in STARCH: CHEMISTRY AND TECHNOLOGY, VOL. III—INDUSTRIALASPECTS, Chpt. XXI—“Production and Use of Pregelatinized Starch”, R. L.Whistler and E. F. Paschall, Ed., Academic Press, New York (1967).

Any starch or starch blend having suitable properties for use herein maybe purified by any method known in the art to remove starch off colorsthat are native to the polysaccharide or created during processing.Suitable purification processes for treating starches are disclosed, forexample, in the family of patents represented by European PatentPublication No. 0 554 818 A2. Alkali washing techniques, for starchesintended for use in either granular or pregelatinized form, are alsouseful and described in the family of patents represented by U.S. Pat.Nos. 4,477,480 and 5,187,272.

Additional suitable starches are starches capable of emulsifying orencapsulating an active ingredient so that there is no need foradditional encapsulating or emulsifying agents. Such starches include,without limitation, hydroxyalkylated starches such as hydroxypropylatedor hydroxyethylated starches, and succinylated starches such as octenylsuccinylated or dodecyl succinylated starches. In one embodiment,emulsifying or encapsulating starches are used so that a solution ordispersion of the film material (starch component, active agent, andoptional additives) may be stored for later processing. Thehydroxyalkylated starches have the added advantage of forming a softerfilm so that there is less or no need for a plasticizer.

Other modified polysaccharides can be used in addition to starch, suchas cellulose, chitin, glucosaminoglyeans, proteoglycans, chitosan,heparin, chondroitin, glycogen and any combination of the foregoing.

The naturally derived water dispersible film forming component can be asingle modified or native starch, single modified cellulosic, a blend ofmodified starches, blend of native starches, blend of modifiedcellulosics, or a blend of both modified starches and cellulosics andnative starches. Blends may be useful for lowering the cost of the filmor for more easily achieving a variety of desirable properties andfunctionalities.

Examples of commercial starches together with their INCI names that maybe used in the present invention as film formers include the following:from National Starch and Chemical Company, AMAZE® polymer (corn starchmodified), CELQUAT® LS-50 resin (polyquaternium-4/hydroxypropyl starchcopolymer), STRUCTURE® XL polymer (hydroxypropyl starch phosphate); fromthe Croda Company, CROSTYLE MFP (trimethyl quaternized maize starch);and from ONDEO Nalco, SENSOMER C1-50 (starch hydroxypropyl trimoniumchloride) and any combination of the foregoing.

A non-limiting example of a commercial cellulosic together with its INCIname that may be used in the present invention as film formers includefrom National Starch and Chemical Company, CELQUAT® LS-50 resin(polyquaternium-4/hydroxypropyl starch copolymer) and any combination ofthe foregoing.

The film forming component of the invention also comprises blends ofboth synthetic and naturally derived water dispersible polymers.

Suitable sunscreen agents or actives useful in the present inventioninclude any particulate sunscreen active that absorbs, scatters, orblocks ultraviolet (UV) radiation, such as UV-A and UV-B. Non-limitingexamples of suitable particulate sunscreen agents include clays, agars,guars, nanoparticles, native and modified starches, modifiedcellulosics, zinc oxide, and titanium dioxide and any combination of theforegoing. Modified starches include, for example, DRY-FLO® PC lubricant(aluminum starch octenylsuccinate), DRY-FLO® AF lubricant (corn starchmodified), DRY-FLO® ELITE LL lubricant (aluminum starch octenylsuccinate(and) lauryl lysine), DRY-FLO® ELITE BN lubricant (aluminum starchoctenylsuccinate (and) boron nitride), all commercially available fromNational Starch and Chemical Company.

In one aspect, the sunscreen agents include those that form a physicaland/or chemical barrier between the UV radiation and the surface towhich they are applied. Non-limiting examples of suitable sunscreenagents include ethylhexyl methoxycinnamate (octinoxate), ethylhexylsalicylate (octisalate), butylmethoxydibenzoylmethane,methoxydibenzoylmethane, avobenzone, benzophenone-3 (oxybenzone),octocrylene, aminobenzoic acid, cinoxate, dioxybenzone, homosalate,methyl anthranilate, octocrylene, octisalate, oxybenzone, padimate O,phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylateand any combination of any of the foregoing

The sunscreen agents can be used in a variety of compositions, includingwithout limitation, cosmetic and personal care compositions, detergentsand household cleaning compositions, paper products, oil fieldchemicals, and food and beverage compositions. Cosmetic and personalcare compositions include skin lotions and creams, skin gels, serums andliquids, facial and body cleansing products, wipes, liquid and bar soap,color cosmetic formulations, make-ups, foundations, sun care products,sunscreens, sunless tanning formulations, shampoos, conditioners, haircolor formulations, hair relaxers, products with AHA and BHA and hairfixatives such as sprays, gels, mousses, pomades, and waxes, includinglow VOC hair fixatives and sunscreens. The compositions can be in anyform, including without limitation, emulsions, gels, liquids, sprays,solids, mousses, powders, wipes, or sticks.

Generally, sunscreen compositions or formulations contain about 0.25 toabout 30% by weight, based on total weight of the composition, of one ormore sunscreen agents/actives or UV filters.

Sunscreen compositions according to the present invention can optionallyfurther include active agents. Suitable active agents include, forexample, anti-acne agents, antimicrobial agents, anti-inflammatoryagents, analgesics, anti-erythemal agents, antiruritic agents,antiedermal agents, antipsoriatic agents, antifungal agents, skinprotectants, vitamins, antioxidants, scavengers, antiirritants,antibacterial agents, antiviral agents, antiaging agents,protoprotection agents, hair growth enhancers, hair growth inhibitors,hair removal agents, antidandruff agents, anti-seborrheic agents,exfoliating agents, wound healing agents, anti-ectoparacitic agents,sebum modulators, immunomodulators, hormones, botanicals, moisturizers,astringents, cleansers, sensates, antibiotics, anesthetics, steroids,tissue healing substances, tissue regenerating substances, hydroxyalkylurea, amino acids, peptides, minerals, ceramides, biohyaluronic acids,vitamins, skin lightening agents, self tanning agents, coenzyme Q10,niacinimide, capcasin, caffeine, and any combination of any of theforegoing.

Sunscreen compositions according to the present invention can optionallyinclude one or more aesthetic enhancers (i.e., a material that impartsdesirable tactile, visual, taste and/or olfactory properties to thesurface to which the composition is applied) and can be eitherhydrophilic or hydrophobic. Non-limiting examples of commercialaesthetic enhancers together with their INCI names that may be used inthe present invention include from National Starch and Chemical Company,PURITY® 21C starch (zea maize (corn) starch) and TAPIOCA PURE (tapiocastarch), as well as combinations thereof.

Sunscreen compositions according to the present invention can optionallyinclude one or more adjuvants, such as pH adjusters, emollients,humectants, conditioning agents, moisturizers, chelating agents,propellants, rheology modifiers and emulsifiers such as gelling agents,colorants, fragrances, odor masking agents, UV stabilizer,preservatives, and any combination of any of the foregoing. Examples ofpH adjusters include, but are not limited to, aminomethyl propanol,aminomethylpropane diol, triethanolamine, triethylamine, citric acid,sodium hydroxide, acetic acid, potassium hydroxide, lactic acid, and anycombination thereof.

Suitable conditioning agents include, but are not limited to,cyclomethicone; petrolatum; dimethicone; dimethiconol; silicone, such ascyclopentasiloxane and diisostearoyl trimethylolpropane siloxy silicate;sodium hyaluronate; isopropyl palmitate; soybean oil; linoleic acid;PPG-12/saturated methylene diphenyldiisocyanate copolymer; urea;amodimethicone; trideceth-12; cekimonium chloride; diphenyl dimethicone;propylene glycol; glycerin; hydroxyalkyl urea; tocopherol; quaternaryamines; and any combination thereof.

Suitable preservatives include, but are not limited to, chlorophenesin,sorbic acid, disodium ethylenedinitrilotetraacetate, phenoxyethanol,methylparaben, ethylparaben, propylparaben, phytic acid, imidazolidinylurea, sodium dehydroacetate, benzyl alcohol,methylehloroisothiazolinone, methylisothiazolinone, and any combinationthereof. The sunscreen composition generally contains from about 0.001%to about 20% by weight of preservatives, based on 100% weight of totalsunscreen composition. In another aspect, the composition contains fromabout 0.1% to about 10% by weight of preservatives, based on 100% weightof total sunscreen composition.

In one aspect sunscreen compositions according to the present inventioninclude a water phase. These sunscreen compositions can also optionallyinclude any cosmetically acceptable solvent. Non-limiting examples ofsuch solvents can include hydrocarbons, alcohols, esters and blendsthereof.

Generally, sunscreen compositions according to the present inventioncontain at least one or more sunscreen actives or agents in an amount ofabout 0.25 to about 30% by weight, based on total weight of thecompositions; one or more film forming polymers in an amount of about0.05 to about 10% by weight, based on total weight of the composition;and heat treated xanthan gum in an amount of about 0.05 to about 20% byweight, based on total weight of the composition, with the remainingcomposition including other ingredients such as the above describedadjuvants, active agents and aesthetic enhancers according to thedesired end formulation. One skilled in the art would know whichadditional ingredients would be required. In another aspect, sunscreencompositions according to the present invention contain one or more filmforming polymers in an amount of about 0.5 to about 5% by weight, basedon total weight of the composition. In even another aspect, sunscreencompositions according to the present invention contain heat treatedxanthan gum in an amount of about 0.05 to about 5% by weight, based ontotal weight of the composition.

The following examples are intended to exemplify the present inventionbut are not intended to limit the scope of the invention in any way. Thebreadth and scope of the invention are to be limited solely by theclaims appended hereto.

EXAMPLES

The formulae described below contain at least two inorganic sunscreenagents—ZnO and TiO₂. Literature teaches that when formulating with boththese types, they should not be in the same phase of the formulation, asagglomeration is likely to occur, resulting in a lower SPF value due toreduction of UV light scattering.

All formulations were prepared according to the follow procedure—

Xanthan gum is dispersed in water until completely hydrated. Theremainder of Phase B less the UVB filter is combined and heated to 75°C., and the UVB filter added. Phase A ingredients are combined and heatto 75° C. Phase A is then added to Phase B and homogenized at 10,000 rpmfor one minute. Cool to room temperature with stirring and add the PhaseC ingredients, with the neutralizer added to adjust the pH to 7.

The results below demonstrate that the combination of both heat treatedxanthan gum (Dehydroxanthan gum) and film-forming polymers(water-dispersible technologies, e.g., acrylates copolymer(s),polyurethanes, etc.) provides an unexpected boost in SPF. Throughseveral experiments detailed here in the Examples, the scope of thisunexpected boost is defined.

Example 1 Comparison of Sunscreen Formulations Containing Heat TreatedXanthan Gum versus Formulations wherein the Xanthan Gum is not HeatTreated

Four sunscreen formulations were prepared as follows:

Ingredient Function Formula 1¹ Formula 2 Formula 3 Formula 4 PHASE AIsohexadecane Emollient 1.5 1.5 1.5 1.5 C12-C15 alkyl benzoate Emollient3.0 3.0 3.0 3.0 Cyclopentasiloxane Emollient 2.25 2.25 2.25 2.25Sorbitan Stearate Emulsifier 1.0 1.0 1.0 1.0 Glyceryl StearateEmulsifier 2.0 2.0 2.0 2.0 (and) PEG-100 Stearate Octocrylene UVB filter2.0 2.0 2.0 1.3 Ethylhexyl Methoxycinnamate UVB filter 7.5 7.5 7.5 5.41Benzophenone-3 UVB filter 3.0 3.0 3.0 2.05 ZnO (and) C12-C15 Alkyl UVA/Bfilter 6.0 6.0 6.0 5.3 Benzoate (and) Polyhydroxystearic Acid PHASE BWater 54.25 54.25 58.65 60.64 Dehydroxanthan Gum Suspension agent, 0.50.0 0.5 0.5 Rheology modifier Xanthan Gum Rheology modifier 0.0 0.5 0.00.0 Acrylates Copolymer Film former 4.4 4.4 0.0 4.4 Glycerin Humectant3.0 3.0 3.0 3.0 TiO₂ and Alumina and Silica UVB filter 7.0 7.0 7.0 5.05and Sodium Polyacrylate PHASE C Corn Starch Modified Aesthetic enhancer2.0 2.0 2.0 2.0 DMDM Hydantoin and Preservative 0.6 0.6 0.6 0.6Iodopropynyl Butylcarbamate Citric Acid (50%) Neutralizer qs to pH 7 qsto pH 7 qs to pH 7 qs to pH 7 TOTAL 100 100 100 100 ¹All values for eachformula provided herein are in weight %, based on total weight of thecomposition or formulation.

The above formulations differ in that Formulation 1 was made with heattreated xanthan gum, Formulation 2 was made with non-heat treatedxanthan gum, and Formulation 3 was made with heat treated xanthan gumbut without the film forming polymer. Formula 4 is based on Formula 1with the exception that the amount of all sunscreen actives (UV filters)has been reduced by 25% to determine whether a reduction in the amountof sunscreen agents will still provide an acceptable SPF value.

In-Vitro SPF Testing Procedure:

These formulations were submitted for in-vitro SPF testing to determineSPF values according to the following procedure—

All formulations were tested for SPF values under confidentiality by anoutside testing laboratory (IMS Inc., Quarry Road Technology Park, 282Quarry Road, Milford Conn., 06460-8508, USA). SPF values were obtainedvia their method entitled IMS Inc In Vitro Sunscreen Waterproof/WaterResistance Protocol for Use with VITRO-SKIN® Substrate. 2 μL/cm² ofsample was applied to the VITRO-SKIN® substrate. The substrate was thenagitated in a 40° C. water bath at 300 rpm for 80 minutes. SPFmeasurements were taken both before and after immersion at 10 differentmeasurements sites using a Labsphere UV 1000S ultraviolet transmittanceanalyzer (Labsphere, Inc. North Sutton, N.H. 03260), with the resultantSPF value calculated as an average. These measurements are compared to ablank in each case (VITRO-SKIN® substrate with no test materialapplied).

Target SPF was 30. Test results provided below show a post-immersionvalue of 32.6 for Formulation 1 (heat treated xanthan gum formulation)versus 20.5 for Formulation 2 (non-heat treated xanthan gumformulation). Formulation 3 containing no acrylates copolymer was madeto see if the combination of heat treated xanthan gum and acrylatescopolymer was needed for a boost in SPF. The resulting SPF value (8.7)indicates that heat treated xanthan gum without the film former does notprovide as effective water resistance in sunscreens as the combinationof the two does. Combination with the film former also results in ahigher pre-immersion or static SPF value, indicating that a better, moreuniform film was formed when dried on the synthetic skin substrate.

TABLE 1 SPF Values Formul- Formul- Formul- Formul- In-vitro Data ation 1ation 2 ation 3 ation 4 Pre-immersion SPF 47.9 49.8 33.9 40.9Post-immersion SPF 32.6 20.5 8.7 35.6 (40 min) 21.4 (80 min)

Formula 4, which contains a 25% reduction in overall UV filterconcentration versus Formula 1, shows a boost to still be quite evident,as 35.6 is close to the 32.6 from the original formulation (based on a40-minute immersion (the time frame used in in-vivo studies to make awater resistance claim in sunscreens according to United Statesguidelines, as opposed to a very water resistant claim that is based onan 80-minute value).

Example 2 UV Filters

The following three formulations were prepared in order to study theeffect of different sunscreen actives and their amount in providing UVprotection—

Form- Form- Form- Ingredient Function ula 5 ula 6 ula 7 PHASE AIsohexadecane Emollient 1.5 1.5 1.5 C12-C15 alkyl benzoate Emollient 3.03.0 3.0 Cyclopentasiloxane Emollient 2.25 2.25 2.25 Sorbitan StearateEmulsifier 1.0 1.0 1.0 Glyceryl Stearate Emulsifier 2.0 2.0 2.0 (and)PEG-100 Stearate Caprylic/Capric Triglyceride Solubilizer 0.0 6.25 6.25Isopropyl Myristate Solubilizer 0.0 6.25 6.25 Octocrylene UVB filter(org) 2.0 0.0 0.0 Ethylhexyl Methoxycinnamate UVB filter (org) 7.5 0.00.0 Benzophenone-3 UVB filter (org) 3.0 0.0 0.0 ZnO (and) C12-C15 AlkylUVA/B filter 0.0 6.0 6.0 (inorg) Benzoate (and) Polyhydroxystearic AcidPHASE B Water 67.25 54.25 58.65 Dehydroxanthan Gum Suspension agent, 0.50.5 0.0 Rheology modifier Xanthan Gum Rheology modifier 0.0 0.0 0.5Acrylates Copolymer Film former 4.4 4.4 4.4 Glycerin Humectant 3.0 3.03.0 TiO₂ and Alumina and Silica UVB filter (inorg) 0.0 7.0 7.0 andSodium Polyacrylate PHASE C Corn Starch Modified Aesthetic enhancer 2.02.0 2.0 DMDM Hydantoin and Preservative 0.6 0.6 0.6 IodopropynylButylcarbamate Citric Acid (50%) Neutralizer qs to pH 7 qs to pH 7 qs topH 7 TOTAL 100 100 100

Formula 5 is similar to Formula 1 with the exception that Formula 5 hasbeen altered to have organic UV filters only (i.e., no inorganicsunscreen actives or agents). Formulation 5 was prepared to understandthe suspension mechanism (as there is nothing to suspend in thisformulation), with the difference in weight from Formula 1 made up withwater.

Formula 6 is similar to Formula 1 with the exception that Formula 6 hasbeen altered to have inorganic UV filters only (i.e., no organicsunscreen actives or agents). Formulation 6 was prepared to determine iforganic UV filters are required to see the SPF boost, with difference inweight from Formula 1 made up with solubilizers of similar polarity tothe organic UV filters. These solubilizers are listed as caprylic/caprictriglyceride (commercially available as Myritol 318) and isopropylmyristate (commercially available as Liponate IPM).

Formula 7 is the same formulation as Formula 6 with the exception thatthe heat treated xanthan gum is replaced with non-heat treated xanthangum as a control.

The following results were determined—

TABLE 2 SPF Values Pre-immersion (static) Post 80-minute immersion SPFvalue SPF Value Formula 5 18.5 5.8 Formula 6 9.2 9.5 Formula 7 10.2 3.4

A lack of inorganic UV filters in Formula 5 results in a reduction inthe static SPF value. Based on the 80-minute immersion SPF value, itappears that the mechanism for SPF boost may be suspension of theinorganic particulate sunscreens, as this formulation has noparticulates to suspend and subsequently shows no SPF boost and limitedretention of organic UV filters. Formula 6 contains only inorganic UVfilters and exhibits approximately 100% SPF retention after 80 minutes.Formula 7, which differs from Formula 6 in that it utilizes traditional(non-heat treated) xanthan gum, does not provide the improvement in SPFretention that Formula 6 gives.

Example 3 Polymers

Two additional formulations were made to test the scope of thefilm-forming polymer chemistry needed to realize the SPF boost. Inaddition to Formula 1, which utilizes polyacrylate chemistry, aformulation with PVP/Eicosene Copolymer (oil dispersible polymer) wasmade as well as one with polyurethane chemistry (water dispersiblepolymer) for comparison.

The two sunscreen formulations were prepared as follows—

Form- Form- Ingredient Function ula 8 ula 9 PHASE A IsohexadecaneEmollient 1.5 1.5 C12-C15 alkyl benzoate Emollient 3.0 3.0Cyclopentasiloxane Emollient 2.25 2.25 Sorbitan Stearate Emulsifier 1.01.0 Glyceryl Stearate Emulsifier 2.0 2.0 (and) PEG-100 StearateOctocrylene UVB filter 2.0 2.0 Ethylhexyl Methoxycinnamate UVB filter7.5 7.5 Benzophenone-3 UVB filter 3.0 3.0 ZnO (and) C12-C15 Alkyl UVA/Bfilter 6.0 6.0 Benzoate (and) Polyhydroxystearic Acid PVP/EicoseneCopolymer Film former 2.0 0.0 PHASE B Water 56.65 53.39 DehydroxanthanGum Suspension agent, 0.5 0.5 Rheology modifier Xanthan Gum Rheologymodifier 0.0 0.0 Acrylates Copolymer Film former 0.0 0.0 GlycerinHumectant 3.0 3.0 TiO₂ and Alumina and Silica UVB filter 7.0 7.0 andSodium Polyacrylate PPG-17/IPDI/DMPA Copolymer Film Former 0.0 5.26PHASE C Corn Starch Modified Aesthetic enhancer 2.0 2.0 DMDM Hydantoinand Preservative 0.6 0.6 Iodopropynyl Butylcarbamate Citric Acid (50%)Neutralizer qs to qs to pH 7 pH 7 TOTAL 100 100

The resulting SPF values were as follows—

TABLE 3 SPF Values Pre-immersion Post-immersion (80 min) (static) SPFvalue SPF Value Formula 1 47.9 32.6 Formula 8 52.9 5.8 Formula 9 50.628.5

From the above results it is seen that there should be at least onefilm-forming polymer present in the water phase that is either waterdispersible or water soluble in order to provide a boost in SPF. ThePVP/Eicosene copolymer, which resides in the oil phase of Formula 8,does not appear to contribute here in the boost or retention of SPF.

Example 4

Formula 10 below is a formulation where ZnO is present in the waterphase and TiO₂ is present in the oil phase:

Form- Ingredient Function ula 10 PHASE A Isohexadecane Emollient 1.5C12-C15 alkyl benzoate Emollient 3.0 Cyclopentasiloxane Emollient 2.25Sorbitan Stearate Emulsifier 1.0 Glyceryl Stearate Emulsifier 2.0 (and)PEG-100 Stearate Octocrylene UVB filter 2.0 Ethylhexyl MethoxycinnamateUVB filter 7.5 Benzophenone-3 UVB filter 3.0 C12-C15 Alkyl Benzoate UVBfilter 10.0 (and) TiO₂ (and) Polyhydroxystearic Acid (and) AluminumStearate (and) Alumina PHASE B Water 52.25 Dehydroxanthan Gum Suspensionagent, 0.5 Rheology modifier Acrylates Copolymer Film former 4.4Glycerin Humectant 3.0 Zinc Oxide UVA/B filter 5.0 PHASE C Corn StarchModified Aesthetic enhancer 2.0 DMDM Hydantoin and Preservative 0.6Iodopropynyl Butylcarbamate Citric Acid (50%) Neutralizer qs to pH 7TOTAL 100

Example 5

Formula 11 below is a sunless tanning formulation with UV filter:

Form- Ingredient Function ula 11 PHASE A Glycerol MonostearateEmulsifier 2.0 PEG-100 Stearate Emulsifier 1.0 Coco-Caprylate/CaprateEmollient 5.0 Cetyl Alcohol Emulsifier 2.0 Dioctyl Adipate Emollient 3.0Cetearyl Alcohol Emulsifier 1.0 Octyl Palmitate Emollient 3.0 SorbitanPalmitate Emollient 0.5 Dimethicone Emollient 0.5 Myristyl MyristateEmollient 1.0 Ethylhexyl UVB filter 7.5 Methoxycinnamate PHASE B Water47.55 Dehydroxanthan Gum Suspension agent, 0.5 Rheology modifierPropylene Glycol Humectant 3.0 Disodium EDTA Chelating agent 0.05Acrylates Copolymer Film Former 4.4 PHASE C Water 5.0 DihydroxyacetoneSelf tanning agent 5.0 PHASE D Corn Starch Modified UV Filter 5.0 MicaInorganic particulate 2.0 Phenoxyethanol (and) Preservative 1.0Methylparaben (and) Ethylparaben (and) Butylparaben (and) Propylparaben(and) Isobutylparaben Citric Acid (50%) qs to pH 4.5 TOTAL 100

Example 6

Formula 12 below is a spray sunscreen formulation:

Form- Ingredient Function ula 12 PHASE A Isohexadecane Emollient 1.5C12-C15 alkyl benzoate Emollient 3.0 Cyclopentasiloxane Emollient 2.25Sorbitan Stearate Emulsifier 1.0 Glyceryl Stearate Emulsifier 2.0 (and)PEG-100 Stearate Octocrylene UVB filter 2.0 Ethylhexyl MethoxycinnamateUVB filter 7.5 Benzophenone-3 UVB filter 3.0 ZnO (and) C12-C15 AlkylUVA/B filter 6.0 Benzoate (and) Polyhydroxystearic Acid PHASE B Water54.7 Dehydroxanthan Gum Suspension agent, 0.05 Rheology modifierAcrylates Copolymer Film former 4.4 Glycerin Humectant 3.0 TiO₂ andAlumina and Silica UVB filter 7.0 and Sodium Polyacrylate PHASE C CornStarch Modified Aesthetic enhancer 2.0 DMDM Hydantoin and Preservative0.6 Iodopropynyl Butylcarbamate Citric Acid (50%) Neutralizer qs to pH 7TOTAL 100

Example 7

Formula 13 below is a whitening formulation with sunscreen actives:

Form- Ingredient Function ula 13 PHASE A Isohexadecane Emollient 1.5C12-C15 alkyl benzoate Emollient 3.0 Cyclopentasiloxane Emollient 2.25Sorbitan Stearate Emulsifier 1.0 Glyceryl Stearate Emulsifier 2.0 (and)PEG-100 Stearate Octocrylene UVB filter 2.0 Ethylhexyl MethoxycinnamateUVB filter 7.5 Benzophenone-3 UVB filter 3.0 PHASE B Water 55.25Dehydroxanthan Gum Suspension agent, 0.5 Rheology modifier AcrylatesCopolymer Film former 4.4 Glycerin Humectant 3.0 PHASE C HydroquinoneWhitening agent 2.0 Water 10.0 PHASE D Corn Starch Modified UV Filter2.0 DMDM Hydantoin and Preservative 0.6 Iodopropynyl ButylcarbamateTOTAL 100

Example 8

Formula 14 below is a whitening formulation with particulates:

Form- Ingredient Function ula 14 PHASE A Steareth-21 Emulsifier 3.0Steareth-2 Emulsifier 1.0 Stearic Acid Emulsifier 4.0 ButylMethoxydibenzoylmethane UVA/B filter 2.0 Ethylhexyl Methoxycinnamate UVBfilter 7.5 Dimethicone Emollient 1.0 Cyclomethicone Emollient 3.0 PHASEB Disodium EDTA Chelating agent 0.1 Water 55.4 Glycerin Humectant 3.5Dehydroxanthan Gum Suspension Agent, 0.5 Rheology Modifier AcrylatesCopolymer Film former 4.4 PHASE C Propylene Glycol Humectant 2.0 CornStarch Modified UV Filter 2.0 Talc Whitening Particulate 10.0 DMDMHydantoin and Preservative 0.6 Iodopropynyl Butylcarbamate TOTAL 100

Example 9

The following formulation was made to investigate the water resistancepotential of a formulation containing only inorganic UV sunscreens(Formula 15). The concentration of the inorganic UV filters wasincreased to maintain similar SPF values. SPF values provided in Table 4below were measured using the same procedure described previously froman outside laboratory.

Inorganic only UV Filter Sunscreen

Form- Ingredient Function ula 15 PHASE A Isohexadecane Emollient 1.5C12-C15 alkyl benzoate Emollient 3.0 Cyclopentasiloxane Emollient 2.25Sorbitan Stearate Emulsifier 1.0 Glyceryl Stearate Emulsifier 2.0 (and)PEG-100 Stearate ZnO (and) C12-C15 Alkyl UVA/B filter 20.0 Benzoate(and) Polyhydroxystearic Acid PHASE B Water 38.75 Dehydroxanthan GumSuspension agent, 0.5 Rheology modifier Acrylates Copolymer Film former4.4 Glycerin Humectant 3.0 TiO₂ and Alumina and Silica UVB filter 23.0and Sodium Polyacrylate PHASE C DMDM Hydantoin and Preservative 0.6Iodopropynyl Butylcarbamate Citric Acid (50%) Neutralizer qs to pH 7TOTAL 100

Example 10

The following formulation was made to investigate the use ofAcrylates/Octylacrylamide Copolymer in this formulation. Similar results(see Table 4) were achieved using this polymer (Formula 16), using thesame in-vitro SPF procedure previously described.

Sunscreen Formulation

Form- Ingredient Function ula 16 PHASE A Isohexadecane Emollient 1.5C12-C15 alkyl benzoate Emollient 3.0 Cyclopentasiloxane Emollient 2.25Sorbitan Stearate Emulsifier 1.0 Glyceryl Stearate Emulsifier 2.0 (and)PEG-100 Stearate Octocrylene UVB filter 2.0 Ethylhexyl MethoxycinnamateUVB filter 7.5 Benzophenone-3 UVB filter 3.0 ZnO (and) C12-C15 AlkylUVA/B filter 6.0 Benzoate (and) Polyhydroxystearic Acid PHASE B Water53.34 Dehydroxanthan Gum Suspension agent, 0.70 Rheology modifierAcrylates/Octylacrylamide Film former 2.0 Copolymer Glycerin Humectant3.0 TiO₂ and Alumina and Silica UVB filter 7.0 and Sodium PolyacrylateTriethanolamine Neutralizer 0.71 PHASE C Aluminum Starch Aestheticenhancer 2.0 Octenylsuccinate DMDM Hydantoin and IodopropynylPreservative 0.6 Butylcarbamate Citric Acid (50%) Neutralizer qs to pH 7TOTAL 100

TABLE 4 SPF Values In-vitro Data Formulation 15 Formulation 16Pre-immersion SPF 48.8 46.8 Post-immersion SPF 48.7 36.6

Example 11 In Vivo Evaluation

Following FDA Final Monograph test methodology for Very Water ResistantSPF, the non-randomized study was conducted as a blind evaluation on 5healthy male/female volunteers with skin types I, II, and/or III. Atimed series of 5 UV doses increasing in 25% increments was administeredto the mid-back. The solar simulator used provides UV radiation between290-400 nm, which is similar to sunlight at sea level. Subjects returnedto the laboratory 22-24 hours later and a trained evaluator gradedresponses of the UV exposed sites on a scale of 0 to 7. This gradingproduced the initial Minimum Erythema Dose (‘MED’). This initial MED isdefined as the lowest UV dose that produces a response grade of 2 (milderythema reaching the borders of the exposed site) or higher.

Adjacent 50 cm² rectangles were drawn on the subject's back. 100 mg oftest product was applied in the designated rectangle and 100 mg of the8% Homosalate control was applied in the remaining rectangle. Productswere applied by “spotting” the material across the area and gentlyspreading until a uniform film was applied to the entire area. After 15minutes post application, the subject was immersed to the upper back ingently moving water that was maintained at 23-32° C. The subjectremained in the water for 20 minutes followed by a 20 minute dryingperiod. This was repeated for a total of 80 minutes immersion.

After the last water immersion, 100 mg of the 8% Homosalate standard wasre-applied and a series of 7 progressively increasing timed UV doseswere given to the site with the test product applied. 15 minutes postapplication of the 8% Homosalate standard, the 7 UV doses were alsogiven. 5 UV doses to an untreated area of the back, increasing by 25%increments, was also given for repeat MED determination, called finalMED.

22-24 hours after UV exposure, the subject returned and was againevaluated. SPF was computed as a ratio of MED for the site treated withproduct versus MED of untreated skin. Static SPF value was reported asratio of MED for the site treated with product versus final MED. Theresults were as follows—

TABLE 5 in vivo SPF Results Formulation 1 Formulation 2 with heatFormulation 3 with regular treated xanthan with only heat xanthan andIn-vivo Data and film former treated xanthan film former Pre 80-minute29 10 19 immersion SPF Post 80-minute 27 9 19 immersion SPF

Example 12 In Vivo Evaluation

Following the same FDA Final Monograph test methodology for Very WaterResistant SPF as listed in the previous example, exception being thenon-randomized study was conducted as a blind evaluation on 3 healthymale/female volunteers. Formulation 15, containing heat treated xanthangum and film former with only inorganic UV filters was tested.

SPF was again computed as a ratio of MED for the site treated withproduct versus MED of untreated skin. Static SPF value was reported asratio of MED for the site treated with product versus final MED. Theresults were as follows—

TABLE 6 in vivo SPF Result Formulation 15 with heat treated In-vivo Dataxanthan and film former Pre 80-minute 23.9 immersion SPF Post 80-minute22.8 immersion SPF

Although the present invention has been described and illustrated indetail, it is to be understood that the same is by way of illustrationand example only, and is not to be taken as a limitation. The spirit andscope of the present invention are to be limited only by the terms ofany claims presented hereafter.

What is claimed is:
 1. Sunscreen composition comprising: one or moresunscreen actives, wherein the one or more sunscreen actives comprisesat least one inorganic sunscreen active; one or more film formingpolymers; and dehydroxanthan gum, wherein at least one film-formingpolymer is present in the water phase of the composition, and whereinthe combination of the dehydroxanthan gum and one or more film formingpolymers result in an SPF enhancement after water immersion. 2.Sunscreen composition according to claim 1 wherein the one or moresunscreen actives are present in an amount of about 0.25 to about 30% byweight, based on total weight of the composition.
 3. Sunscreencomposition according to claim 1 wherein the one or more film formingpolymers are present in an amount of about 0.05 to about 10% by weight,based on total weight of the composition.
 4. Sunscreen compositionaccording to claim 1 wherein the heat treated dehydroxanthan gum ispresent in an amount of about 0.05 to about 20% by weight, based ontotal weight of the composition.
 5. Sunscreen composition according toclaim 1 wherein the one or more inorganic sunscreen actives comprises atleast zinc oxide and/or titanium dioxide.
 6. Sunscreen compositionaccording to claim 1 wherein at least one of the one or more inorganicsunscreen actives is in a water phase of the composition.
 7. Sunscreencomposition according to claim 1 wherein the one or more film formingpolymers comprises at least an acrylates copolymer.
 8. Sunscreencomposition according to claim 1 wherein the one or more film formingpolymers comprises at least a polyurethane copolymer.
 9. Sunscreencomposition according to claim 1 wherein the composition is anoil-in-water emulsion.
 10. Sunscreen composition according to claim 1wherein the one or more sunscreen actives comprises at least one or moreparticulates chosen from clays, agars, guars, nanoparticles, native andmodified starches, modified cellulosics, zinc oxide, titanium dioxideand combinations thereof.
 11. Sunscreen composition according to claim10 wherein the modified starches comprises at least an octenyl succinate(OSA) modified starch, modified corn starch and combinations thereof.12. Sunscreen composition according to claim 1 wherein the one or moresunscreen actives comprises at least one organic sunscreen active. 13.Sunscreen composition according to claim 12 wherein the at least oneorganic sunscreen active is selected from the group consisting ofethylhexyl methoxycinnamate (octinoxate), ethylhexyl salicylate(octisalate), butylmethoxydibenzoylmethane, methoxydibenzoylmethane,avobenzone, benzophenone-3 (oxybenzone), octocrylene, aminobenzoic acid,cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octocrylene,octisalate, oxybenzone, padimate O, phenylbenzimidazole sulfonic acid,sulisobenzone, trolamine salicylate and combinations thereof. 14.Sunscreen composition according to claim 1 further comprising one ormore active agents.
 15. Sunscreen composition according to claim 14wherein the active agents are selected from the group consisting ofanti-acne agents, antimicrobial agents, anti-inflammatory agents,analgesics, anti-erythemal agents, antiruritic agents, antiedemalagents, antipsoriatic agents, antifungal agents, skin protectants,vitamins, antioxidants, scavengers, antiirritants, antibacterial agents,antiviral agents, antiaging agents, protoprotection agents, hair growthenhancers, hair growth inhibitors, hair removal agents, antidandruffagents, anti-seborrheic agents, exfoliating agents, wound healingagents, anti-ectoparacitic agents, sebum modulators, immunomodulators,hormones, botanicals, moisturizers, astringents, cleansers, sensates,antibiotics, anesthetics, steroids, tissue healing substances, tissueregenerating substances, amino acids, peptides, minerals, ceramides,hydroxyalkyl urea, biohyaluronic acids, vitamins, skin lighteningagents, self tanning agents, coenzyme Q10, niacinimide, capcasin,caffeine, and combinations thereof.
 16. Sunscreen composition accordingto claim 1 further comprising one or more adjuvants.
 17. Sunscreencomposition according to claim 1 further comprising one or moreconditioning agents.
 18. Sunscreen composition according to claim 1further comprising one or more preservatives.
 19. Sunscreen compositionaccording to claim 1 further comprising one or more aesthetic enhancers.20. Sunscreen composition according to claim 19 wherein the one or moreaesthetic enhancers is selected from the group consisting of cornstarch, tapioca starch and combinations thereof.
 21. Method of reducingUV radiation on a substrate comprising applying to the substrate aneffective amount of the sunscreen composition according to claim
 1. 22.Sunscreen composition according to claim 1 wherein the dehydroxanthangum has a moisture content of less than about 8%.